EP0173879B1 - Polyethers having tertiary alcoholic terminals - Google Patents
Polyethers having tertiary alcoholic terminals Download PDFInfo
- Publication number
- EP0173879B1 EP0173879B1 EP85109981A EP85109981A EP0173879B1 EP 0173879 B1 EP0173879 B1 EP 0173879B1 EP 85109981 A EP85109981 A EP 85109981A EP 85109981 A EP85109981 A EP 85109981A EP 0173879 B1 EP0173879 B1 EP 0173879B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyethers
- formula
- terminals
- hydroxyl
- active hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000570 polyether Polymers 0.000 title claims description 24
- 230000001476 alcoholic effect Effects 0.000 title description 6
- -1 hydroxyl compound Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 2
- 150000002118 epoxides Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000010944 pre-mature reactiony Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical group 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
- Hydroxyl terminated polyethers find uses as raw materials of polyurethane and polyester resins. Other uses include cosmetics, plasticizers, surfactants and raw materials of these products. Conventional polyethers are terminated with primary or secondary alcoholic groups, the presence of which normally contributes to their desirability for intended uses. It has been experienced in certain cases that the primary or secondary alcohol function is too active and therefore the presence thereof is not desirable. For example, polyethers having too active alcoholic function can lead to a premature reaction when reacted with polyisocyanates. Attempts have been made to remove the hydroxyl function by blocking with a group such as methyl or acyl, or replacing the hydroxyl group with chlorine. Obviously, polyethers having blocked or chlorinated terminals are not suitable for uses in which the presence of hydroxyl function is essential, e.g. for the production of polyurethane and polyester resins.
- The DE-A-2 250 937 discloses polyethers which are terminated by a hydroxyl group. However, only polyethers having one tertiary OH-group at one terminal end are disclosed. Said known polyesters are used as tensides.
- It is therefore an object of the present invention to provide new hydroxyl terminated polyethers which are free from the foregoing defects and therefore less active than conventional hydroxyl terminated polyethers.
- The polyethers of the present invention lead to polyurethanes with surprisingly improved physical properties and flame retardancy.
- According to the present invention, these objects have been achieved by providing polyethers of the formula:
- R is the residue of an organic hydroxyl compound or primary or secondary amine compound having a plurality of active hydrogen atoms, said plurality of active hydrogen atoms being removed.
- R, is a C,-C,o alkyl or aryl,
- R2 is a Cl-Clo alkyl,
- R3 is H, CH3, C2H5 or phenyl,
- x is 5-100,
- y is 1-5, and
- z is 2-8.
- The polyethers of the present invention are prepared by reacting a compound of the formula:
- The compounds of the formula II generally correspond to conventional polyethers having terminal primary or secondary alcoholic moieties and are synthesized by the well-known addition reaction of C2―C4 alkylene oxide or styrene oxide to a starting hydroxyl or amine compound having two to eight active hydrogen atoms in the presence of a basic or acidic catalyst.
- Examples of starting hydroxyl or amine compounds include di- or polyhydroxyl compounds such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, glycerine, trimethylolpropane, pentaerythritol, sorbitol and sucrose, di- or polyamines such as ethylenediamine, hexamethylenediamine and tetramethylenepentamine.
- About 5 to 100 moles per active hydrogen atom of alkylene oxide and/or styrene oxide may be reacted with the starting hydroxyl or amine compound to give the polyethers of the formula II as is well-known in the art. When these polyethers of the formula II contain different recurring units, these units may form either random or block copolymer.
- The resulting polyethers of the formula II may be reacted with about 1 to 5 moles per hydroxyl group of an epoxide of the formula:
- The polyethers of the present invention have at their each terminal end a tertiary alcoholic moiety which is less active than primary or secondary alcoholic terminals possessed by conventional polyethers. Accordingly, they are highly suitable, for example, for preparing polyisocyanate-containing formulations wherein premature reactions should be avoided without compromising properties of the resulting polyurethane resins.
- The invention is further illustrated by the following examples wherein all parts and percents are by weight.
- An autoclave having stirring means was charged with 76 parts of propylene glycol and 5 parts of potassium hydroxide, and then purged with nitrogen gas. Then 924 parts of propylene oxide were introduced at a pressure of 3 kg/cm2 (about 3 bar) and reacted at 130°C. Thereafter 72 parts of isobutylene oxide were introduced to the autoclave at a pressure of 1 kg/cm2 (about 3 bar) and reacted at 130°C for 4 hours. After the reaction, 20 parts of synthetic aluminum silicate was added and the mixture stirred at 120°C at the atmospheric pressure for 3 hours. The mixture was then removed from the reactor and filtered through a one micron filter. 960 parts of polyether having a viscosity of 250 pPas at 25°C were obtained.
- Similar to Example 1, the polyethyers of this invention were produced from varying starting hydroxyl or amine compounds. Table 1 shows details of the reaction conditions.
- A specimen of a polyurethane resin was produced using the reaction product obtained in Example 1. As a control, a corresponding specimen was produced using conventional polypropylene glycol having a molecular weight of 1,000.
- Table 2 shows details of the procedure and properties of these specimens.
Claims (6)
1. Polyethers of the following general formula:
wherein
R is the residue of an organic hydroxyl compound or of a primary or secondary amine compound having a plurality of active hydrogen atoms, said plurality of active hydrogen atoms being removed.
R1 is a C1―C10 alkyl or aryl,
R2 is a C1―C10 alkyl,
R3 is H, CH3, C2H5 or phenyl,
x is 5-100,
y is 1-5, and
z is 2-8.
2. Polyethers of claim 1, wherein R2 is methyl and R1 is methyl or phenyl.
3. Polyethers of claim 2, wherein R3 is H or CH3.
4. A process for preparing the polyethers of claims 1-3, comprising reacting a compound of the formula
with an epoxide of the formula:
in the presence of a basic or acidic catalyst.
5. A process of claim 4, wherein the reaction temperature is 100-150°C.
6. The use of the polyethers of anyone of claims 1-3 in polyurethane formulations.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59167377A JPS6144924A (en) | 1984-08-09 | 1984-08-09 | Production of low-activity polyoxyalkylene compound |
| JP167377/84 | 1984-08-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0173879A1 EP0173879A1 (en) | 1986-03-12 |
| EP0173879B1 true EP0173879B1 (en) | 1989-04-05 |
Family
ID=15848583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85109981A Expired EP0173879B1 (en) | 1984-08-09 | 1985-08-08 | Polyethers having tertiary alcoholic terminals |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4703114A (en) |
| EP (1) | EP0173879B1 (en) |
| JP (1) | JPS6144924A (en) |
| DE (1) | DE3569251D1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037969A (en) * | 1986-07-03 | 1991-08-06 | Takeda Chemical Industries, Ltd. | Glycosyl derivatives and use thereof |
| US4859358A (en) * | 1988-06-09 | 1989-08-22 | The Procter & Gamble Company | Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection |
| GB2219596A (en) * | 1988-06-09 | 1989-12-13 | Procter & Gamble | Liquid automatic dishwashing compositions having enhanced stability |
| US4988452A (en) * | 1988-06-09 | 1991-01-29 | The Procter & Gamble Company | Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant |
| US5003111A (en) * | 1989-02-14 | 1991-03-26 | Arco Chemical Technology, Inc. | Isobutylene oxide polyols |
| EP0403718A3 (en) * | 1989-06-20 | 1991-12-27 | Ciba-Geigy Ag | Products of styrene oxide |
| US5232628A (en) * | 1989-09-27 | 1993-08-03 | Ciba-Geigy Corporation | Polyadducts of alkylene oxide and styrene oxide with aryl alkanols |
| EP0420807A1 (en) * | 1989-09-27 | 1991-04-03 | Ciba-Geigy Ag | Addition products of alkylene and styrene oxide on arylalkanols |
| US5227533A (en) * | 1989-10-04 | 1993-07-13 | Isp Investments Inc. | Alk-1-enyl ethers |
| US5225606A (en) * | 1989-10-04 | 1993-07-06 | Isp Investments Inc. | Alk-1-enyl ethers |
| US5243089A (en) * | 1989-10-04 | 1993-09-07 | Isp Investments Inc. | Alk-1-enyl ethers |
| ATE117665T1 (en) * | 1990-11-14 | 1995-02-15 | Oreal | AMPHIPHILES, NON-IONIC DERIVATIVES OF GLYCERIN AND THE CORRESPONDING INTERMEDIATE PRODUCTS, METHOD FOR THEIR PRODUCTION AND COMPOSITIONS CONTAINING THEM. |
| WO2006038724A1 (en) * | 2004-10-06 | 2006-04-13 | Nof Corporation | Cosmetic bases and cosmetics containing the same |
| WO2010011961A2 (en) * | 2008-07-25 | 2010-01-28 | University Of Georgia Research Foundation, Inc. | Prokaryotic rnai-like system and methods of use |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH327719A (en) * | 1952-07-08 | 1958-02-15 | Wyandotte Chemicals Corp | Manufacturing process for surfactants |
| US2886600A (en) * | 1957-03-29 | 1959-05-12 | Dow Chemical Co | Process for producing isobutyl ethers |
| SE319903B (en) * | 1964-01-31 | 1970-01-26 | Pharmacia Ab | |
| GB1036175A (en) * | 1964-06-30 | 1966-07-13 | Shell Int Research | Improvements in or relating to polyurethane foam |
| US3374277A (en) * | 1965-10-20 | 1968-03-19 | Hercules Inc | Diol of poly |
| DE2250937A1 (en) * | 1972-10-18 | 1974-04-25 | Basf Ag | Low-foam, alkali-resistant surfactants - addition products of higher oxo alcohols and ethylene-, propylene- and butylene -oxides for use in washing up or metal cleaning compsns. |
| US4275244A (en) * | 1978-05-11 | 1981-06-23 | Basf Wyandotte Corporation | Linear polyalkylene ether glycols of high molecular weight |
| DE2925628A1 (en) * | 1979-06-26 | 1981-01-22 | Huels Chemische Werke Ag | CONNECTIONS SUITABLE FOR LOWING THE INTERFACE VOLTAGE OF OILY PHASES AGAINST WATER |
| DE3219822A1 (en) * | 1982-05-26 | 1983-12-01 | Bayer Ag, 5090 Leverkusen | SINGLE-PHASE, STABLE, SALTY POLYOL COMPOSITIONS WITH A HIGH ETHYLENE GLYCOL OR BUTANDIOL CONTENT AND THEIR USE FOR THE PRODUCTION OF POLYURETHANES |
-
1984
- 1984-08-09 JP JP59167377A patent/JPS6144924A/en active Granted
-
1985
- 1985-08-08 EP EP85109981A patent/EP0173879B1/en not_active Expired
- 1985-08-08 DE DE8585109981T patent/DE3569251D1/en not_active Expired
- 1985-08-09 US US06/764,042 patent/US4703114A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Saunders/Frisch, Polyurethanes I, 34,35,73 (1978) * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3569251D1 (en) | 1989-05-11 |
| JPS6144924A (en) | 1986-03-04 |
| US4703114A (en) | 1987-10-27 |
| EP0173879A1 (en) | 1986-03-12 |
| JPH0458495B2 (en) | 1992-09-17 |
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